Treatment of cellulosic material



Patented June 4,

UNITED STATES PATENT OFFICE TREATMENT OF CELLULOSIC MATERIAL- John Gwynant Evans, Henry Alfred Piggott, Reginald John William Reynolds, John Donald Rose, and Eric Everard Walker, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application June 23, 1938, Serial No. 215,495. In Great Britain June 30, 1937 6 Claims. (01. 8120) The present invention relates to a process of links may themselves treatment of cellulosic material whereby it is trogen atoms. rendered capable or being dyed with acid wool According to the invention cellulosic material dyestuffs or acid chrome dyestuffsthe dyeings so is treated at a relatively low temperature with obtained being fast to washing or other aqueous a solution of a compound constituted as described treatments. when necessary in the presence of or subsequent- By cellulosic material We mean any material 1y with formaldehyde or a substance capable of consisting of or containing natural cellulose fibre yi d g fo e in t Conditions Of reacsuch as cotton, linen or jute, or regenerated celtion. and is then heated for a short time to a lulose fibre or filament, either spun, woven or in moderately e e ated te pe atu ethe form of paper or cardboard; we include also AS eompOllnds Coming under e above regenerated cellulose in the form of film. scription as containing the groups (A) and (B) It is an object of the invention to make it posthere spoken of, there come to be mentioned those sible to dye cellulosic materials with the classes o t e e a m a of dyestuffs known as acid wool dyestuffs and H m acid chrome dyestuffs. As is known, these are R R R N(X) L CO NH2 characterised by the presence of sulphonic and/or wherein the Symbols used, so far as they do not carboxylic acid groups other dy t ff are carry their known and customary significance, known, equally capable of dyeing Wool. These are explained belowcontain other acid groups 6' g" the sulphuric R stands for hydrogen or an alkyl, aralkyl or ester group. These also are regarded as acid aryl radical and and Rm Stand for the wool dyestuffs for the purposes of this invention. same dlfierent alkyl aralyl radicals? or The invention is particularly adapted to the RIRJ'R'HN taken by itself may Stand for a tiary amine, which is a heterocyclic compound,

dyeing of regenerated cellulose as by its means that fibre can be given affinity foracid dyestuffs. typlfied by pyndme of the one class, or the alkyl piperidines of another; or R."R"NH taken by Thus the dyeing of viscose staple fibre materials, especially mixed fibr and union yams of itself may stand for a heterocyolic secondary amine, e. g. piperidine.

cose staple fibre and wool, is facilitated.

The invention comprises the application to L stands for the lmk spoken of above be linked by oxygen or ni- 30 cellulosic material of a compound in the molecule it Stands for divalent organic radical for of which there is at least one of each of two kinds Stance: of functional groups. These two functional CH2-CONH,

groups are (A) an ammonium or similar group capable of so interacting during dyeing with a dyestufi of the kind described so that, as is supposed, the material carries or encloses within its intermicellar or other interstices pigmentary substance which can be regarded as an organic salt of the dyestuff acid; and (B) a group originally such that the compound is water soluble but so adapted to self orconjoint reaction on application of heat that the heating treatment referred to results in the fixation on the material of a substance no longer containing group (B) but still 45 containing group (A). i

More particularly group (B) is such that it is capable of reacting with formaldehyde. Suitable groups classified under (13) are such that the compound is a carboxylic amide, a substitute urea or a carbamate.

In these compounds the functional groups (A) and (B) may be linked together by arylene or alkylene radicals which may provide the entire link, or may be part of a link, e. g., alkylene X stands for an acid radical.

Compounds suitable to be used in the process of the invention may conveniently be made by the processes described in British Patents Nos. 497,043; 497,368, and 497,485.

It is a further feature of the invention to use, instead of the compounds represented by the general formulae given above the suitable products of their condensation with formaldehyde, for example, their methylol derivatives. As will be seen, here a preformed formaldehyde compound is used, but the treatment may nevertheless be carried out in presence of a further quantity of formaldehyde or formaldehyde yielding substance.

As suitable formaldehyde yielding substances thcre may be mentioned, for example, dimethylol urea, the dimethyl ether of dimethylol urea and methylol urethane.

The invention is carried into practical effect in a number of ways. Thus (a) the cellulosic material is impregnated with a solution, for example. an aqueous solution of one of the compounds mcntioned, the solution containing also formaldehyde or a formaldehyde yielding substance. The impregnated material is then dried and subjected to a short heat treatment. If desired, the drying and heating treatment may be carried out in one step.

(b) The cellulosic material is impregnated with a solution of one or more of the said compounds and exposed in the wet or dry state to formaldehyde vapour at atmospheric or higher pressure, preferably at elevated temperature.

(0) The cellulos ic material is with a solution of one or more of the compounds mentioned, then, preferably after drying, is treated in a bath containing formaldehyde or a formaldehyde yielding substance, dried, and finally subjected to a short heat treatment. Again if necessary, the drying and heat treatment may be carried out as one step.

(d) When using pre-formed condensation products, such as the methylol compounds mentioned, the treatment is carried out by any of the foregoing methods, or the simultaneous or subsequent treatment with formaldehyde or a formaldehyde-yielding substance may be omitted, as already explained.

The impregnation mentioned may be carried out with advantage by use of an acidified liquor containing e. g., boric acid, acetic acid, tartaric acid, lactic acid, tannic acid or an acid substance or compound which yields acid under the conditions of drying or heating, e. g., ammonium dihydrogen phosphate, ammonium chloride, ammonium thiocyanate or sodium bisulphite. The heat-treatment may also be carried out in acid conditions by application of acid as vapour or in other ways. I

The heat treatment above referred to may be for a short period, for example, 5 to 30 minutes, f

at a temperature of 100-i40 C. Alternatively it may be provided by steaming the treated material for a short time, for example, V to 1 hour.

The invention is illustrated but not limited by the following examples, in which the parts are by weight.

Example 1 Finely woven cotton material of the kind known as limbric is impregnated at room temperature with a solution containing 2 parts of the condensation product of formaldehyde and fl-ureidoethylpyridinium chloride of the formula C5H5N (Cl) --CH2CH2-NHCONH2 and 0.3-part of ammonium dihydrogen phosphate in 98 parts of water. The material is squeezed to remove excess of liquor and is then dried rapidly in a current of warm air at a temperature of 60 C. The dry fabric is heated for 5 minutes at a temperature of 120 C. After heating the fabric is well rinsed in warm Water. may now be dyed with acid wool colours.

For example, 100 parts of treatedcotton is rinsed in water and entered at 40-50 C. into 20 The dye is almost completely exhausted from the dyebath, the treated material being dyed toa impregnated v The material full red shade. The dyeing shows good resistance to water and to washing treatments.

Alternatively, 100 parts of the treated cotton may be dyed-in a bath containing 1 part of C00- massie Violet 2R (Colour Index No. 758), 3 parts of acetic'acid and 10 parts of sodium sulphate in 3000 parts of water, using the dyeing conditions described above. The material is thus dyed to a full violet shade which has good resistance to water and to soap washing.

Example 2 Viscose rayon fabric is soaked in a solution containing 2 parts of ureidoethylpyridinium chloride of the formula 0.3 part of ammonium dlhydrogen phosphate and 3.0 parts of a 40% aqueous solution of formaldehyde in 100 parts of cold water. The material is squeezed until it contains its own weight of solution and is dried in a current of hot air at 60 C. It is then heated for V hour at 140 C. The material now has enhanced afiinity for acid wooldyestuifs. 'It may be dyed, for example with Coomassie Violet 2R (Colour Index No. 758) by the method described in the previous example.

. Example 3 Viscose rayon stockinette is soaked in a solu- 'tion containing 2 parts of .carbamylmethylpyri .dinium chloride of the formula 0.3 part of ammonium dihydrogen phosphate and 12.5 parts of a 40% aqueous formaldehyde solution in 100 parts of cold water. The material is squeezed until-it contains its own weight of the solution and is dried in a current of hot air at 60 C. It is then heated for hour at 140 C. The material now has affinity for acid wool dyestuffs and acid chrome dyestuffs and may be dyed therewith in the manner normally used for W001 dyeing. Moreover the dyeings 'so obtained are fast to washing and other aqueous treatments.

For example, 100 parts of viscose rayon stockinette treated as described with either of the above agents may be dyed for 1 hour at the boil in a solution containing 2 parts of Azo Geranine 2G (Colour Index No. 31) 3 parts of concentrated sulphuric acid and 10 parts of sodium sulphate in 3000parts of water. There is thus produced a full red shade which is very fast to aqueous soap washing treatments.

If, in the above process, instead of the carbamylmethylpyridinium chloride, there is used an equal weight of p dimethylaminophenylurea methosulphate of formula there is similarly obtained a fabric possessing afiinity for acid wool dyestuffs.

If viscose fabric impregnated as described with eitherof the above agents, instead of being heated Viscose rayon fabric is soaked in a solution containing 2 parts of hydroxymethylcarbamylmethylpyridinium chloride of the formula C5H5N (C1) CH2CONHCH2OH in parts of water and is then squeezed so that it retains its own weight of the solution. -It is then heated, without previous drying, to 140 C. for hour. The material now has affinity for acid wool dyestuffs and can be dyed therewith in the manner normally used for wool dyeing. 1'

Thus, for example, 100 parts of the treated viscose are dyed for 1 hour at the boil in a bath containing 2 parts of Tartrazine N (Colour Index No. 640), 3 parts of concentrated sulphuric acid, 10 parts of sodium sulphate and 3000 parts of water. The dyeing so obtained has a full yellow shade which is fast to aqueous soap washing.

Example 5 Viscose staple fibre is soaked in a solution containing 2 parts of carhamylmethylpridinium chloride, 0.3 part of ammonium dihydrogen phosphate and 12.5 parts of a 40% aqueous formaldehyde solution in 100 parts of water. The fibre is squeezed so that it contains its own weight of the solution and is then dried in a current of hot air at C. Finally, it is heated for hour at 140 C. The fibre now has aflinity for acid wool colours and acid chrome colours and may be dyed therewith by the methods normally used for dyeing wool.

Thus, for example, parts of the treated viscose fibre are dyed for 1 hour at the boil in a bath containing 2 parts of Naphthalene Orange G (Colour Index No. 151), 3 parts of concentrated sulphuric acid, 10 parts of sodium sulphate and 3000 parts of water. The fibre is thus dyed to a full orange shade which is fast to aqueous soap washing treatments.

Alternatively 100 parts of the treated fibre are dyed for 1 hour at the boil in a bath containing B parts of Solochrome Black WDFA (Colour Index No. 203), 3 parts of 30% aqueous acetic acid, 10 parts of sodium sulphate and 3000 parts of water. 200 parts of an aqueous 1% solution of sulphuric acid are then added and the bath is maintained at the boil for a further 15 minutes. 300 parts of an aqueous 1% solution of potassium dichromate are now added and the bath is maintainTe'd at the boil for a further hour. Theflbre is then removed from the bath, rinsed and dried. It is thus dyed to a full black shade which is fast to aqueous soap washing treatments.

Example 6 parts of a 40% aqueous formaldehyde solution in 100 parts of water. The fabric is squeezed until it retains its own weight of the solution and is then heated for hour at C. The material now has aillnity for acid wool colours and acid chrome colours.

Thus, for example, it may be dyed for 1 hour at the boil in a bath containing 2 parts of Coomassie Navy Blue ZRN (Colour Index No. 289), 0.5 part of potassium dichromate and 3000 parts of water. The material is then rinsed and dried. It is thus dyed a deep blue shade which has good iastn'ess to aqueous soap washing.

We cla-imi 1. A process for enhancing the afllnity of cellu- I losic material for acid wool dyestufis and acid chrome dyestuffs which comprises treating the said material with a solution of an organic compound selected from the class consisting of carboxylic amides, substituted ureas, and carbamates, said compound having the general formula RRR"N(X)-L-CONH2 wherein RR'R"N as a whole represents the entire molecular structure of an amine selected from the class consisting of aliphatic secondary amines, heterocyclic secondary amines, aliphatic tertiary amines,mixed tertiary amines, and heterocyclic tertiary amines, X stands for an acid radical, and L stands for a divalent organic radical selected from the group: --CH2, CHzCONH-, CH2CH2NH-, -CH2CH2O-, and -CsH4NH; and the Iormaldehyde condensation products of said carboxylic amides, substituted ureas, and carbamates, and then heating the so impregnated material for a short time to a moderately elevated temperature suilicient to cause said organic compound to become fixed on the said cellulosic material.

2. A process as set forth in claim 1 wherein the impregnating solution also contains a substance selected from the class consisting of formaldehyde and formaldehyde yielding substances.

3. A process as set forth in claim 1 wherein the impregnating solution also contains a substance selected from the class consisting of acids and acid yielding substances.

4 A process as set forth in claim 1 wherein the substituted urea which is employed is beta ureidoethylpyridinium chloride.

5. A process as set forth in claim 1 wherein the substituted urea which is employed is p-di-= methylamin'ophenylurea methosulphate.

6. A process as set forth in claim 1 whereinthe carboxylic amide which is employed is carbamylmethylpyridinium chloride.

JOHN GWYNANT EVANS.

HENRY ALFRED PIGGO'IT.

REGINALD JOHN WILLIAM YNOLDS. JOHN DONALD ROSE.

ERIC EVERARD WALKER. 

